EFFECTS OF SCALE ON LAND USE AND WATER QUALITY RELATIONSHIPS: A LONGITUDINAL BASIN‐WIDE PERSPECTIVE1

ABSTRACT: Human land use is a major source of change in catchments in developing areas. To better anticipate the long‐term effects of growth, land use planning requires estimates of how changes in land use will affect ecosystem processes and patterns across multiple scales of space and time. The complexity of biogeochemical and hydrologic interactions within a basin makes it difficult to scale up from process‐based studies of individual reaches to watershed scales over multiple decades. Empirical models relating land use/land cover (LULC) to water quality can be useful in long‐term planning, but require an understanding of the effects of scale on apparent land use‐water quality relationships. We empirically determined how apparent relationships between water quality and LULC data change at different scales, using LIJLC data from the Willapa Bay watershed (Washington) and water quality data collected along the Willapa and North Rivers. Spatial scales examined ranged from the local riparian scale to total upstream catchment. The strength of the correlations between LTJLC data and longitudinal water quality trends varied with scale. Different water quality parameters also varied in their response to changes in scale. Intermediate scales of land use data generally were better predictors than local riparian or total catchment scales. Additional data from the stream network did not increase the strength of relationships significantly. Because of the likelihood of scale‐induced artifacts, studies quantifying land use‐water quality relationships performed at single scales should be viewed with great caution.     

Variations in expression of carbon isotope fractionation of chlorinated ethenes during biologically enhanced PCE dissolution close to a source zone

The stable carbon isotope values of tetrachloroethene (PCE) and its degradation products were monitored during studies of biologically enhanced dissolution of PCE dense nonaqueous phase liquid (DNAPL) to determine the effect of PCE dissolution on observed isotope values. The degradation of PCE was monitored in a 2-dimensional model aquifer and in a pilot test cell (PTC) at Dover Air Force Base, both with emplaced PCE DNAPL sources. Within the plume down gradient from the source, the isotopic fractionation of dissolved PCE and its degradation products were consistent with those observed in biodegradation laboratory studies. However, close to the source zone significant shifts in the isotope values of dissolved PCE were not observed in either the model aquifer or PTC due to the constant input of newly dissolved, non fractionated PCE, and the small isotopic fractionation associated with PCE reductive dechlorination by the mixed microbial culture used. Therefore the identification of reductive dechlorination in the presence of PCE DNAPL was based upon the appearance of daughter products and the isotope values of those daughter products. An isotope model was developed to simulate isotope values of PCE during the dissolution and degradation of PCE adjacent to a DNAPL source zone. With the exception of very high degradation rate constants (>1/day) stable carbon isotope values of PCE estimated by the model remained within error of the isotope value of the PCE DNAPL, consistent with measured isotope values in the model aquifer and in the PTC.     

Trophic dynamics of U, Ni, Hg and other contaminants of potential concern on the Department of Energy’s Savannah River Site

The Department of Energy’s Savannah River Site is a former nuclear weapon material production and current research facility located in South Carolina, USA. Wastewater discharges from a fuel and nuclear reactor target manufacturing facility released depleted and natural U, as well as other metals into the Tims Branch-Steed Pond water system. We investigated the current dynamics of this system for the purposes of environmental monitoring and assessment by examining metal concentrations, bioavailability, and trophic transfer of contaminants in seven ponds. Biofilm, detritus, and Anuran and Anisopteran larvae were collected and analyzed for stable isotopes (δ ¹⁵N, δ ¹³C) and contaminants of potential concern (COPC) with a focus on Ni, U, and Hg, to examine metal mobility. Highest levels of Ni and U were found in biofilms U (147 and 332 mg kg^?1 DW, respectively), while highest Hg levels were found in tadpoles (1.1 mg kg^?1 DW). We found intraspecific biomagnification of COPCs as expressed through stable isotope analysis. Biofilms were the best indicators for contamination and Anuran larvae with the digestive tract removed were the best indicators of the specific bioavailability of the focal metals. Monitoring data showed that baseline δ ¹⁵N values differed between ponds, but within a pond, values were stable throughout tadpole Gosner stage, strengthening the case to use this species for monitoring purposes. It is likely that there still is risk to ecosystem integrity as COPC metals are being assimilated into lower trophic organisms and even low levels of this mixture has shown to produce deleterious effects to some wildlife species.     

Dechlorination after thermal treatment of a TCE-contaminated aquifer: laboratory experiments

A microcosm study was conducted to evaluate dechlorination of trichloroethene (TCE) to ethene and survival of dechlorinating bacteria after a thermal treatment in order to explore the potential for post-thermal bioremediation. Unamended microcosms containing groundwater and aquifer material from a contaminated site dechlorinated TCE to cis-1,2-dichloroethene (cDCE), while lactate-amended microcosms dechlorinated TCE to cDCE or ethene. A thermal treatment was simulated by heating a sub-set of microcosms to 100 degrees C for 10d followed by cooling to 10 degrees C over 150 d. The heated microcosms demonstrated no dechlorination when unamended. However, when amended with lactate, cDCE was produced in 2 out of 6 microcosms within 300 d after heating. Dechlorination of TCE to cDCE thus occurred in fewer heated (2 out of 12) than unheated (10 out of 12) microcosms. In unheated microcosms, the presence of dechlorinating microorganisms, including Dehalococcoides, was confirmed using nested PCR of 16S rRNA genes. Dechlorinating microorganisms were detected in fewer microcosms after heating, and Dehalococcoides were not detected in any microcosms after heating. Dechlorination may therefore be limited after a thermal treatment in areas that have been heated to 100 degrees C. Thus, inflow of groundwater containing dechlorinating microorganisms and/or bioaugmention may be needed for anaerobic dechlorination to occur after a thermal treatment.     

Quantification of biotransformation of chlorinated hydrocarbons in a biostimulation study: added value via stable carbon isotope analysis

Stable carbon isotope analysis of chlorinated aliphatic compounds was performed at an in situ biostimulation pilot test area (PTA) at a site where 1,2-dichloroethane (1,2-DCA) and trichloroethene (TCE) were present in groundwater. Chlorinated products of TCE reductive dechlorination (cis-dichloroethene (cDCE) and vinyl chloride (VC)) were present at concentrations of 17.5 to 126.4 micromol/L. Ethene, a potential degradation product of both 1,2-DCA dihaloelimination and TCE reductive dechlorination was also present in the PTA. Emulsified soybean oil and lactate were added as electron donors to stimulate anaerobic dechlorination in the PTA. Stable carbon isotope analysis provided evidence that dechlorination was occurring in the PTA during biostimulation, and a means of monitoring changes in dechlorination efficiency over the 183 day monitoring period. Stable carbon isotope analysis was also used to determine if ethene production in the PTA was due to dechlorination of TCE, 1,2-DCA, or both. Fractionation factors (alpha) were determined in the laboratory during anaerobic biotransformation of 1,2-DCA via a dihaloelimination reaction in four separate enrichment cultures. These alpha values (as well as the previously published ranges of alpha for the dechlorination of TCE, cDCE and 1,2-DCA) were used, along with isotopic values measured during the pilot test, to derive quantitative estimates of biotransformation during the pilot test. Dechlorination was found to account for 10.7 to 35.9%, 21.9 to 74.9%, and 54.4 to 67.8% of 1,2-DCA, TCE and cDCE concentration loss respectively in the PTA. Stable carbon isotope analysis indicates that dechlorination of 1,2-DCA, TCE and cDCE were all significant processes during the pilot test, while ethene production during the pilot test was dominated by 1,2-DCA dihaloelimination. This study demonstrates how stable carbon isotope analysis can provide more conservative estimates of the extent of biotransformation than do conventional protocols. In addition, in a complex mixed plume such as this, compound specific isotope analysis is shown to be one of the few methods available for clarifying dominant biotransformation pathways where breakdown products are non-exclusive (i.e. ethene).     

Development of a field method for measuring manganese in welding fume

Workers who perform routine welding tasks are potentially exposed to fume that may contain manganese. Manganese may cause respiratory problems and is implicated in causing the occurrence of Parkinson-like symptoms. In this study, a field colorimetric method for extracting and measuring manganese in welding fume was developed. The method uses ultrasonic extraction with an acidic hydrogen peroxide solution to extract welding fume collected on polyvinyl chloride filters. Commercially available pre-packaged reagents are used to produce a colored solution, created by a reaction of manganese(ii) with 1-(2-pyridylazo)-2-naphthol. Absorbance measurements are then made using a portable spectrophotometer. The method detection limit and limit of quantification (LOQ) were 5.2 microg filter(-1) and 17 microg filter(-1), respectively, with a dynamic range up to 400 microg filter(-1). When the results are above the LOQ for the colorimetric method, the manganese masses are equivalent to those measured by the International Organization for Standardization Method 15202-2, which employs a strong acid digestion and analysis using inductively coupled plasma-optical emission spectrometry.